Patent GB-1101866-A (GB)
Title: Pyroglutamic acid derivatives and polymers thereof
IPC: C07D207/28
Filed: 1965-03-01
Abstract: Polymers and copolymers of the compounds of formulae <FORM:1101866/C3/1> <FORM:1101866/C3/2> <FORM:1101866/C3/3> <FORM:1101866/C3/4> where n is 0 or 1; R is H or CH3 with the proviso that when n is 0, R is H; Ra is H or CH3; X is (1) hydrogen, ammonium, a protonated amine or cation of a metal from Groups I, II or III of the Periodic Table or (2) a monovalent hydrocarbon group; x is an integer equal to the valency of the group X, Y is NH2 or the residue of a primary or secondary amine; and Q is the residue of a polyamine with 2 or more primary or secondary amino groups (see Division C2) are prepared by conventional polymerization methods using catalyst in bulk, emulsion or suspension processes.  The copolymers may be between the monomers above, or with at least one of the monomers with a-CH = CB< group. Examples describe the polymerization of N-vinyl methyl pyroglutamate with t.-butyl peroxide or a a 1-azobisisobutyronitrile catalysts; N-vinyl butyl pyroglutamate; N-vinyl octyl pyroglutamate; and N-vinyl octadecyl pyroglutamate; the copolymerization of N-vinyl octyl pyroglutamate and methyl methacrylate; N-vinyl methyl pyroglutamate and N-vinyl butyl pyroglutamate; N-vinyl methyl pyroglutamate and N-vinyl pyrrolidone acrylonitrile, vinyl acetate, maleic anhydride, methyl methacrylate, and styrene; N-ally (ally pyroglutamate) and methyl methacrylate; and N-allyl methyl pyroglutamate and methyl methacrylate. The preparation of polyvinyl sodium pyroglutamate, and the hydrolysis of polyvinyl methyl pyroglutamate; the copolymer of N-vinyl methyl pyroglutamate and N-vinyl butyl pyroglutamate; and the copolymer of N-vinyl methyl pyroglutamate and N-vinyl pyrrolidone and the preparation of polyvinyl pyroglumatic acid hydrazide are also described.  The products are water-soluble or water-insoluble according to the proportions of comonomers and may be used as soil conditioners or soil suspending agents, impregnating or coating agents, as up-graders for natural oils, or as laundering agents.ALSO:Additives for soya-bean oil and other low unsaturated vegetable oils to upgrade them for use in paints varnishes and lacquers, comprise N-alkenyl pyrogentamate monomers of formulae <FORM:1101866/C4-C5/1> <FORM:1101866/C4-C5/2> <FORM:1101866/C4-C5/3> <FORM:1101866/C4-C5/4> and copolymers thereof with ethylenically unsaturated monomers, where n is 0 or 1; R is H or CH3 with the proviso that when n is O, R is H; Ra is H or CH3; X is (1) hydrogen, ammonium, a protonated amine or cation of a metal from Groups I, II or III of the Periodic Table or (2) a monovalent hydrocarbon group; x is an integer equal to the valency of the groups X, Y is NH2 or the residue of a primary or secondary amine; and Q is the residue of a polyamine with 2a more primary or secondary amino groups (see Division C2).ALSO:The invention comprises compounds of the formulae <FORM:1101866/C2/1> wherein n is 0 or 1, R is H or CH3 but when n is 0, R is H, Ra is H or CH3, X is hydrogen, ammonium, a protonated amine or cation of a Group I, II or III metal or a monovalent hydrocarbon group, x is an integer equal to the valency of X, Y is NH2 or the residue of a primary or secondary amine and Q is the residue of a polyamine with 2 or more primary or secondary amino groups, specifically hydrocarbyl, e.g. alkyl, alkenyl esters or an amide of N-vinyl pyroglutamic acid or metal salts or an amine addition salt thereof, and bis(N-vinyl pyroglutamic acid) diamide are mentioned and compounds claimed are N-vinyl pyroglutamic acid, methyl, ethyl, butyl, sodium, potassium, lithium and ammonium pyroglutamates, N-vinyl pyroglutamide, N-vinyl pyroglutamic acid hydrazide and semicarbazide, 1,11-methylene bis-(allyl pyroglutamate), 1,11-methylene bis-(methallyl pyroglutamate), and mixed allyl and methallyl diester of 1,11-bis-methylene-pyroglutamic acid.  The compounds may be prepared by reacting a hydrocarbon pyroglutamate with a vinylating, allylating, or methallylating agent for instance by reacting the N-sodium or potassium salt with acetylene, or with vinyl, allyl or methallyl chloride or an alkyl vinyl ether with a mercuric or zinc salt transvinylation catalyst. The other derivatives mentioned are prepared by the conventional methods. The compounds may be polymerized or copolymerized (see Division C3).ALSO:Pills and tablets are coated with polymers or copolymers derived from N-alkenyl pyroglutamates of formul <FORM:1101866/A5-A6/1> <FORM:1101866/A5-A6/2> <FORM:1101866/A5-A6/3> <FORM:1101866/A5-A6/4> wherein n is 0 or 1; R is H or CH3 with the proviso that when n is O, R is H; R is H or CH3; X is (1) hydrogen, ammonium, a protonated amine or cation of a metal from Groups I, II, or III of the Periodic Table or (2) a monovalent hydrocarbon group; x is an integer equal to the valency of the group X, Y is NH2 or the residue of a primary or secondary amine; and Q is the residue of a polyamine with 2 or more primary or secondary amino groups (see Division C2).  A composition of a copolymer of N-vinyl pyrrolidone and N-vinyl methyl pyroglutamate, which may include glycerine is described in examples as a water-soluble protective medium for pills. Hair-setting sprays may also include water-soluble copolymers derived from the above monomers.